EP2501758B1 - Élastomère thermoplastique pour des applications à froid et à l'état humide - Google Patents

Élastomère thermoplastique pour des applications à froid et à l'état humide Download PDF

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EP2501758B1
EP2501758B1 EP10782479.9A EP10782479A EP2501758B1 EP 2501758 B1 EP2501758 B1 EP 2501758B1 EP 10782479 A EP10782479 A EP 10782479A EP 2501758 B1 EP2501758 B1 EP 2501758B1
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ethylene
olefin
composition
interpolymer
inventive
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EP2501758A1 (fr
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Laura Bauerle Weaver
Ashish Batra
Kim L. Walton
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene

Definitions

  • the invention relates to a thermoplastic elastomer composition rich in ethylene/a-olefin polymer content or propylene- ⁇ -olefin content, and more particularly to thermoplastic elastomer profiles for use in cold and/or wet applications.
  • Gaskets are used in a variety of applications, for example in appliances, such as refrigerators and freezers, each requiring a flexible gasket for sealing the area between the door and appliance body.
  • One of the most commonly used materials for the production of gaskets is polyvinyl chloride (PVC).
  • PVC gaskets become brittle at low temperatures and cracking becomes a problem, and installation at lower temperatures is also difficult. Also, an unpleasant odor is present during compounding and extrusion of PVC, and when the finished gaskets are removed from packaging prior to installation.
  • PVC is not considered an environmentally friendly material because it involves the use of the following: vinyl chloride monomer production, phthalate plasticizers, heat stabilizers, and processing lubricants that may contain heavy metals.
  • PVC-based gaskets may give rise to disposal concerns as well as potential release of toxic materials in the event of incineration. Therefore, there is a need for a material to replace PVC-based profiles, particularly those used in large home appliances such as refrigerator and freezer gaskets, washing machines, dryers and dishwashers, and which satisfies the required specifications, and has improved processability and environmental friendliness.
  • Other applications of such polymeric materials could include, for example, molded articles, overmolded articles, and tubing.
  • thermoplastic elastomers used for profiles demands that several properties be balanced. These include low viscosity at processing shear rates, ability to freeze quickly as the profile leaves the die so dimensional stability can be maintained, a certain compression set for elastic recovery under transportation and use conditions, ability to heat weld, and a certain softness for better sealing properties.
  • Production of TPEs for profile applications has required rheological modification steps, such as peroxide modification of the thermoplastic elastomer or dynamic vulcanization, or use of expensive ingredients such as styrene block copolymer (SBC)-rich compounds, in order to balance the required end-use properties.
  • SBC styrene block copolymer
  • WO 98/32795 relates to rheology-modified thermoplastic elastomer compositions and articles fabricated therefrom. Therefore, there remains a need for a TPE for profile use that meets all of the specifications to replace PVC-based profiles, while simplifying production and design of the TPEs.
  • the invention provides a composition comprising:
  • the invention provides a second composition comprising:
  • Certain embodiments of the second compositions satisfy certain relationships between tan delta (tan ⁇ ) and viscosity (referred to as shape retention index or "SRI”) over an extended temperature range.
  • Some embodiments of the second compositions provide polymer compositions meeting specific tensile modulus, elongation, compression set at -10 °C and 40 °C, UV resistance, weight reduction on heating, Vicat softening temperature, water resistance, split tear resistance, anti-microbial resistance, weight loss on cooling/heating cycle, odor, weld strength, chemical and oil resistance, tactile feel, and crystallization temperature, as may be specified by various OEMs of relevant end-use appliances.
  • inventive second compositions do not utilize formulated thermoplastic vulcanates or rheology-modified, reactive-extruded blends, or TPEs rich in styrenic polymers. That is, the inventive second compositions do not contain more than 50 wt% thermoplastic vulcanate and/or styrenic polymers based on the total thermoplastic elastomer composition weight.
  • Component C comprises an ethylene/a-olefin-diene interpolymer, or blends thereof.
  • Component C in some embodiments of the invention, comprise blends of one or more ethylene/a-olefin copolymers and one or more ethylene/a-olefin -diene interpolymers.
  • Ethylene/ ⁇ -olefin interpolymers including ethylene/ ⁇ -olefin-diene interpolymers, useful in various embodiments of the invention have a ⁇ Hf greater than, or equal to, 36 J/g. All values of ⁇ Hf greater than, or equal to, 36 J/g are disclosed and included herein.
  • the ethylene/a-olefin interpolymers useful in the invention alternatively, may have, for example, a ⁇ Hf greater than, or equal to, 37 J/g; or, in the alternative, greater than, or equal to, 38 J/g.
  • Ethylene/ ⁇ -olefin interpolymers useful in component C have a Mooney Viscosity greater than, or equal to, 55. All values of Mooney Viscosity of greater than, or equal to, 55 are included and disclosed herein. Ethylene/ ⁇ -olefin interpolymers useful in the invention have a Mooney viscosity of greater than or equal to 55; in the alternative, greater than or equal to 57; in the alternative, greater than or equal to 59; or in the alternative, greater than or equal to 60; or in the alternative, greater than or equal to 61.
  • ⁇ -olefin monomers useful in the ethylene/ ⁇ -olefin copolymers and interpolymers of component C may be selected, in certain embodiments, from the group of C 3 -C 20 ⁇ -olefins.
  • Preferred ⁇ -olefins for use in certain embodiments of the invention are designated by the formula CH 2 CHR*, where R* is a linear or branched alkyl group of from 1 to 12 carbon atoms.
  • suitable ⁇ -olefins include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
  • a particularly preferred ⁇ -olefin is propylene
  • Suitable dienes for use in the ethylene/a-olefin-diene interpolymers of components A and C include conjugated or non-conjugated, straight or branched chain-, cyclic- or polycyclic-dienes comprising from 4 to 20 carbons.
  • Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene.
  • the ethylene/a-olefin-diene interpolymer has a molecular weight distribution (MWD) from 2 to 4. All values and sub-ranges from 2 to 4 are included and disclosed herein; for example, ethylene/a-olefin/diene interpolymer may have an upper limit of MWD of 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8 or 4 and an MWD lower limit of 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8.
  • the MWD of the ethylene/a-olefin/diene interpolymer may be from 2 to 4; in the alternative, from 2.5 to 3.5; in the alternative, from 2.8 to 3.8; or in the alternative, from 2.1 to 3.9.
  • the ethylene/a-olefin-diene interpolymer has a % crystallinity (%Cry) from 13 to 20%, by weight. All values and sub-ranges from 13 %Cry to 20 %Cry are included and disclosed herein; for example the ethylene/a-olefin/diene interpolymer %Cry may have an upper limit of 14%, 15%, 16%, 17%, 18%, 19% or 20% by weight, and an ethylene/a-olefin-diene interpolymer %Cry lower limit of 13%, 14%, 15%, 16%, 17%, 18%, or 19% by weight.
  • the %Cry of the ethylene/a-olefin/diene interpolymers useful in the invention may be from 13% to 20% by weight; in the alternative, from 14% to 19% by weight; in the alternative, from 15% to 18% by weight; or in the alternative, from 16% to 20% by weight.
  • the ethylene/a-olefin-diene polymers have an ethylene content of from 50% to 70% by weight, a propylene content from 20% to 49% by weight, and a nonconjugated diene content from 1% to 10% by weight, all weight percentages based upon the total weight of the polymer. All values and sub-ranges from 50 to 70 wt% ethylene content in the ethylene/a-olefin/diene interpolymer are included and disclosed herein.
  • the ethylene/a-olefin/diene interpolymer may have a lower limit of 50, 55, 60, or 65 wt % ethylene and an upper limit of 55, 60, 65, or 70 wt% ethylene.
  • the ethylene/ ⁇ -olefin/diene polymer may have a lower limit of 20, 25, 30, 35, 40 or 45 wt % propylene and an upper limit of 25, 30, 35, 40 or 49 wt% propylene.
  • All values and sub-ranges of 1 to 10 wt% diene content in the ethylene/a-olefin/diene interpolymer are included and disclosed herein.
  • the ethylene/a-olefin/diene interpolymer may have a lower limit of 1, 3, 5, 7 or 9 wt % diene and an upper limit of 2, 4, 6, 8 or 10 wt% diene.
  • the ethylene/a-olefin/diene interpolymer has a rheology ratio (V0.1/V100), at 190 °C, greater than or equal to 25. All values of the ethylene/a-olefin/diene interpolymer rheology ratio of greater than or equal to 25 are included and disclosed herein; for example the ethylene/a-olefin/diene interpolymer rheology ratio, at 190 °C, may alternatively be greater than or equal to 30; in the alternative, greater than or equal to 35; in the alternative, greater than or equal to 39; in the alternative, greater than or equal to 41; in the alternative, greater than or equal to 45; or in the alternative, greater than or equal to 50.
  • the ethylene/a-olefin interpolymer is an EPDM.
  • component C comprises an ethylene/propylene/diene (EPDM) interpolymer, or blend thereof.
  • EPDM ethylene/propylene/diene
  • the EPDM interpolymer contains from 20% to 80% by weight of ethylene, from 19% to 70% by weight of a higher ⁇ -olefin, and from 1% to 10% by weight of a nonconjugated diene.
  • the more preferred higher ⁇ -olefins are propylene and 1-butene.
  • the more preferred polyenes are ethylidene norbornene, 1 ,4-hexadiene, and dicyclopentadiene .
  • EPDM interpolymers for use examples include Nordel IP 4770R/P, Nordel IP 4760, Nordel IP 4785 and Nordel IP 3760P Hydrocarbon Rubbers available from Dow Chemical. Keltan polymers available from DSM Elastomers Americas, Baton Rouge, La., VISTALON EP(D)M ethylene/propylene rubber of EPDM interpolymers available from ExxonMobil Chemical or ROYALENE EPDM available from Lion Copolymers, LLC. Particularly useful are EPDM with a Mooney Viscosity greater than equal to 50.
  • the ethylene/a-olefin/diene interpolymer is not oil extended.
  • the ethylene/a-olefin/diene interpolymer is in the form of free-flowing pellets.
  • free-flowing refers to the ability of the pellets (of typical polymer pellet sizes) to move or flow at ambient conditions, without adhering together to form larger masses.
  • the ethylene/ ⁇ -olefin/diene interpolymer is formed using a single site catalyst.
  • the single site catalyst is selected from a metallocene catalyst, a constrained geometry catalyst, or a post metallocene catalyst.
  • the single site catalyst is selected from a constrained geometry catalyst, or a post metalllocene catalyst.
  • the ethylene/ ⁇ -olefin/diene interpolymer is formed using a constrained geometry catalyst.
  • the ethylene/ ⁇ -olefin/diene interpolymer is formed using a post metalllocene catalyst.
  • the ethylene/ ⁇ -olefin/diene interpolymer has a molecular weight distribution (MWD) less than 3.5, preferably less than 3.2, and more preferably less than 3.1.
  • the ethylene/ ⁇ -olefin/diene interpolymer is diluted with a minor amount of oil and/or process additive, such that the oil and/or additive level is less than 33% of the weight of the polymer in the pre-compounded state.
  • the ethylene/ ⁇ -olefin/diene interpolymer is not diluted with an oil or process additive in the pre-compounded state.
  • the ethylene/ ⁇ -olefin/diene interpolymer comprises at least two ethylene/a-olefin/diene interpolymers, and preferably two interpolymers.
  • at least one interpolymer has a crystallization temperature (Tc) less than 35°C, preferably less than 30°C, and more preferably less than 25°C
  • the overall ethylene/a-olefin/diene interpolymer has a crystallization temperature (Tc) greater than 20°C, preferably greater than 25°C, and more preferably greater than 28°C.
  • At least one interpolymer has a Mooney Viscosity (ML 1+4, 125°C) from 30 to 100, preferably 40 to 90, and the overall ethylene/a-olefin/diene interpolymer has a Mooney Viscosity (ML 1+4, 125°C) from 50 to 100, preferably 50 to 90.
  • at least one interpolymer has a MWD from 1.5 to 3
  • the overall ethylene/a-olefin/diene interpolymer has a MWD from 2 to 3.5.
  • each interpolymer is an EPDM, and preferableythe diene is 5-ethylidene-2-norbornene (ENB).
  • the ethylene/a-olefin/diene interpolymer may comprise a combination of these embodiments.
  • the ethylene/ ⁇ -olefin/diene interpolymer is an in-reactor blend of at least two polymers, and preferably two polymers.
  • the ethylene/ ⁇ -olefin/diene interpolymer is a post-reactor blend of at least two polymers, and preferably two polymers.
  • the ethylene/ ⁇ -olefin/diene interpolymer is an EPDM.
  • the diene is ENB.
  • the ethylene/ ⁇ -olefin/diene interpolymer may comprise a combination of two or more embodiments as described herein.
  • An ethylene/ ⁇ -olefin interpolymer may comprise a combination of two or more embodiments as described herein.
  • An ethylene/ ⁇ -olefin copolymer may comprise a combination of two or more embodiments as described herein.
  • An ethylene/ ⁇ -olefin-diene interpolymer may comprise a combination of two or more embodiments as described herein.
  • Embodiments of the inventive second composition comprise at least one HDPE.
  • the properties of the high density polyethylene (HDPE) useful in certain embodiments of the invention vary depending upon the desired application.
  • the molecular weight of the HDPE for use in certain embodiments of the invention varies depending upon the application, but may be indicated using a melt flow measurement I 2 is inversely proportional to the molecular weight of the polymer. The higher the molecular weight, the lower the I 2 , although the relationship is not linear.
  • High-density polyethylene useful in component D of certain embodiments of the invention may have a density in the range from 0.94 to 0.96 g/cc. All individual values and sub-ranges from 0.94 to 0.96 g/cc are included herein and disclosed herein; for example, the high-density polyethylene composition may have a lower limit density of 0.94 g/cc, 0.945 g/cc, 0.95 or 0.955 g/cc and an upper limit density of 0.945 g/cc, 0.949 g/cc, 0.955 g/cc or 0.96 g/cc.
  • the high-density polyethylene may have a density in the range of 0.940 to 0.950 g/cc; or in the alternative, from 0.95 to 0.96 g/cc; or in the alternative, from 0.945 to 0.960 g/cc.
  • the high-density polyethylene has an I 2 from 1 to 50 g/10min. All values and sub-ranges from 1 to 50 g/10 min are disclosed and included herein; for example, the high-density polyethylene composition may have an I 2 lower limit of 1, 10, 20, 30, 40 or 45 g/10 min and an upper limit of 5, 15, 25, 35, 45, or 50 g/10 min.
  • the high-density polyethylene has an I 2 from 1 to 50 g/10 min; or in the alternative, from 20 to 40 g/10 min; or in the alternative, from 30 to 43 g/10 min; in the alternative, from 5 g/10 min to 30 g/10 min; or in the alternative, from 5 to 46 g/10 min.
  • Molecular weight distribution (Mw/Mn) of the HDPE can be narrow or broad, e.g., Mw/Mn from 2 to as high as 40. All individual ranges from 2 to 40 are included and disclosed herein: for example, the HDPE may have a lower limit of Mw/Mn of 2, 5, 10, 13, 23 or 36 and an upper limit of Mw/Mn of 5, 12, 20, 27, 33, 39, or 40.
  • the HDPE may be present in an amount from 30 to 100 PHR, based on the weight of the ethylene/a-olefin interpolymer. All values and sub-ranges from 30 to 100 PHR are included and disclosed herein; for example the HDPE may be present at an upper limit of 40, 50, 60, 70, 80, 90 or 100 PHR and at a lower limit of 30, 40, 50, 60, 70, 80, or 90 PHR.
  • the amount of HDPE may range, for example, from 30 to 70 PHR; in the alternative, from 30 to 60 PHR; in the alternative, from 30 to 40 PHR; in the alternative from 40-80 PHR; in the alternative, from 60 to 90 PHR; or in the alternative from 60 to 85 PHR.
  • the HDPE may be produced by any process including metallocene, Cr and Ziegler- Natta catalyst processes. Any conventional ethylene homopolymerization or copolymerization reactions may be employed to produce the high-density polyethylene useful in embodiments of the invention. Such conventional ethylene homopolymerization or copolymerization reactions include gas phase polymerization, slurry phase polymerization, liquid phase polymerization, and combinations thereof using conventional reactors, e.g. gas phase reactors, loop reactors, stirred tank reactors, and batch reactors.
  • conventional reactors e.g. gas phase reactors, loop reactors, stirred tank reactors, and batch reactors.
  • An HDPE may comprise a combination of two or more embodiments as described herein.
  • One embodiment of the inventive second compositions is further characterized by a hardness in the range of 40-85 Shore A, tensile strength from 2 to 8 MPa, elongation > 400%, and compression set at 40 °C from 30 to 75%.
  • the ethylene/a-olefin/diene interpolymer has a rheology ratio (V0.1/V100), at 190°C, greater than, or equal to 25.
  • the HDPE has an I 2 from 1 to 50 g/ 10 min, preferably from 5 g/10 min to 30 g/ 10 min.
  • Vulcanization agents include peroxides, azo compounds, phenols, azides, aldehyde-amine reaction products, substituted ureas, substituted guanidines; substituted xanthates; substituted dithiocarbamates; sulfur-containing compounds, such as thiazoles, imidazoles, sulfonamides, thiuramidisulfides, paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; silanes. See Encyclopedia of Chemical Technology, Vol. 17, 2nd edition, Interscience Publishers, 1968 ; also Organic Peroxides, Daniel Seem, Vol. 1, Wiley-Interscience, 1970 ); and C. P.
  • an inventive second composition does not comprise a free radical coagent.
  • the free radical coagent is a monomer or low molecular weight polymer having two or more functional groups with high response to free radicals. Typically, these functional groups are either methacrylate, allyl or vinyl.
  • Free radical coagents include diallyl terephthalate, triallylcyanurate, triallylisocyanurate, 1,2 polybutadiene, divinyl benzene, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate,allyl methacrylate, N N'-m-phenylene bismaleimide, toluene bismaleimide -p-quinone dioxime, nitrobenzene, diphenylguanidine.
  • the inventive second composition comprises ethylene/a-olefin/diene interpolymer and HDPE.
  • the ethylene/a-olefin/diene interpolymer is EPDM.
  • the diene is ENB.
  • the ethylene/a-olefin/diene interpolymer is present in an amount greater than the amount of the HDPE.
  • the ethylene/ ⁇ -olefin/diene interpolymer is EPDM.
  • the diene is ENB.
  • the weight ratio of the ethylene/a-olefin/diene interpolymer to the HDPE is from 2 to 5, preferably from 2.2 to 4, more preferably from 2.5 to 3.5.
  • the ethylene/a- olefin/diene interpolymer is an EPDM.
  • the diene is ENB.
  • the elastomeric polymer, component C comprises a diene.
  • the ethylene/ ⁇ -olefin interpolymer has a ⁇ Hf greater than, or equal to, 36 J/g, preferably greater than, or equal to, 38 J/g.
  • the ethylene/ ⁇ -olefin interpolymer is an ethylene/ ⁇ -olefin/diene interpolymer.
  • the HDPE is present in an amount from 30 to 100 PHR, based on the weight of the ethylene/ ⁇ -olefin interpolymer.
  • a second composition comprising: i) component C, an ethylene/a-olefin interpolymer, optionally comprising a third comonomer, wherein the interpolymer has a Mooney Viscosity (ML 1+4, 125 °C) greater than, or equal to, 55 and ⁇ Hf greater than, or equal to, 36 J/g; and ii) component D, a high density polyethylene (HDPE).
  • ML 1+4, 125 °C Mooney Viscosity
  • HDPE high density polyethylene
  • the second composition provides a composition in accordance with any of the preceding embodiments, except that wherein the second composition is further characterized by an SRI less than or equal to 1.5 at 10000 Pa-s, and less than 4.5 at 1000 Pa-s for compositions with TMA greater than 85°C.
  • the second composition provides a composition in accordance with any of the preceding embodiments, except that component C has a MWD less than 4.
  • the ethylene/ ⁇ -olefin interpolymer is an ethylene/ ⁇ -olefin/diene interpolymer.
  • the ethylene/ ⁇ -olefin/diene interpolymer has a rheology ratio (V0.1/VI 00), at 190°C, greater than, or equal to 25.
  • the HDPE has an I 2 from 1 to 50 g/10 min, or from 5 to 40 g/10 min, or from 10 to 20 g/10 min.
  • the second composition provides a composition in accordance with any of the preceding embodiments, except that the HDPE is present in an amount from 30 to 100 PHR, based on the weight of the ethylene/ ⁇ -olefin interpolymer.
  • the second composition provides a composition in accordance with any of the preceding embodiments, except that the second composition further comprises an oil.
  • the second composition provides a composition in accordance with any of the preceding embodiments, except that the second composition further comprises a filler.
  • the invention further provides an article comprising at least one component formed from the composition of any one of the preceding embodiments.
  • the inventive article has a tack force less than, or equal to, 0.012 N.
  • the inventive article is in accordance with any of the preceding embodiments, except that the article has a compression set, at 70 °C, less than 70 percent, as measured by ASTM D-395.
  • inventive second composition further comprise an oil.
  • Some embodiments of the inventive second composition further comprise a filler.
  • Some embodiments of the inventive article have a tack force less than, or equal to, 0.012 N.
  • Some embodiments of the inventive article have a compression set, at 70°C, less than 70 percent.
  • Embodiments of the invention provide polyolefin-based inventive compositions, further including additives and fillers to produce a rheological behavior to replace PVC-based profiles while meeting the performance properties demanded by the intended end-use application.
  • One embodiment of the inventive second composition is further characterized by a hardness in the range of 40-85 Shore A, tensile strength from 2 to 8 MPa, elongation > 400%, and compression set at 40 °C from 30 to 75%.
  • the second composition comprises at least one ethylene/a- olefin interpolymer, component C, wherein the interpolymer has a Mooney Viscosity greater than, or equal to, 55 and ⁇ Hf greater than, or equal to, 36 J/g; and component D, at least one high density polyethylene (HDPE).
  • component C wherein the interpolymer has a Mooney Viscosity greater than, or equal to, 55 and ⁇ Hf greater than, or equal to, 36 J/g
  • component D at least one high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • One embodiment of the second composition is characterized by an SRI less than or equal to 1.6 at 10000 Pa-s, and less than 4.5 at 1000 Pa-s for compositions with TMA at 1000 ⁇ m greater than 85°C.
  • One embodiment of the second composition comprises a component c having a MWD less than 3.
  • One embodiment of the second composition comprises a component c having a MWD less than 2.5.
  • One embodiment of the second composition comprises a component c having a MWD less than 2.
  • One embodiment of the second composition comprises a component c having a MWD in the range from 1 to 3.
  • One embodiment of the second composition comprises a component c having a MWD in the range from 1.5 to 3.
  • the inventive compositions further comprise an oil.
  • Oils useful in embodiments of the invention include, for example, a paraffinic oil, aromatic oil, napththenic oil, hydrogenated (white) oil (such as,. Kaydol oil), vegetable and animal oil and their derivatives, petroleum derived oils or a combination thereof.
  • the oil present may be in an amount from 50 to 200 PHR (based on the weight of the ethylene/a-olefin interpolymer).
  • the oil amount may have a lower limit of 50, 70, 90, 110, 130, 150, 170, or 190 PHR and an upper limit of 60, 80, 100, 120, 140, 160, 180 or 200 PHR.
  • the oil may be present in an amount from 50 to 200 PHR; in the alternative, from 50 to 130 PHR; in the alternative, from 70 to 180 PHR; in the alternative, from 80 to 120 PHR; or in the alternative, from 130 to 190 PHR.
  • additives include surface tension modifiers, flame retardants, scratch and mar modifying additives, anti-block agents, slip additives (including a wide variety of primary amides, secondary amides and secondary bis-amides, such as oleamides, erucamides and stearamides), lubricants, antimicrobial agents (such as organometallics, isothazolones, organosulfurs and mercaptans); antioxidants (such as phenolics, secondary amines, phosphites and thioesters); antistatic agents (such as quaternary ammonium compounds, amines, and ethoxylated, propoxylated or glycerol compounds); hydrolytic stabilizers; lubricants (such as fatty acids, fatty alcohols, esters, fatty amides, metallic stearates, paraffinic and microcrystalline waxes, silicones and orthophosphoric acid esters); mold
  • a hindered phenolic antioxidant is IrganoxTM 1076 antioxidant, available from BASF.
  • a composition further comprises polydimethysiloxane.
  • polydimethylsiloxane may be present in an amount from 0 to 0.5 wt%, based on the total weight of the thermoplastic elastomer composition.
  • compositions disclosed herein may comprise at least one filler which can be used to adjust, for example, volume, weight, costs, and/or technical performance.
  • fillers useful in various embodiments of the invention include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina trihydrate, glass microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof.
  • the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fiber, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fiber or a mixture thereof.
  • the fillers disclosed in U.S. Pat. No. 6,103,803 and Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, pages 901-948 (2001 ) may also be used in various embodiments of the invention.
  • the amount of the filler in the inventive composition may be from 20 to 200 PHR (based on weight of ethylene/a-olefin interpolymer). All values and sub-ranges from 20 to 200 PHR are disclosed and included herein; for example, the filler may be present from an upper limit of 30, 60, 90, 120, 150, 170 or 200 PHR and from a lower limit of 20, 50, 80, 110, 140, 170 or 190 PHR.
  • the filler may be present in an amount ranging from 20 to 100 PHR; in the alternative, from 40 to 180 PHR; in the alternative, from 60 to 150 PHR; or in the alternative, from 100 to 130 PHR.
  • an adsorptive inorganic additive may improve the odor properties of the products provided herein though no odor issues exist with the specific examples mentioned herein.
  • an odor absorber additive such as charcoal, calcium carbonate or magnesium oxide in the range from 0.1 to 3 weight percent, or 0.5 to 2 weight percent, based on the total composition, is effective in eliminating odors.
  • the inventive compositions disclosed herein optionally comprise at least one UV stabilizer that may prevent or reduce the degradation of the inventive compositions by UV radiations.
  • Any UV stabilizer known to a person of ordinary skill in the art may be added to the inventive compositions disclosed herein.
  • suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, metallic salts, zinc compounds and combinations thereof.
  • the amount of the UV stabilizer in the inventive composition can be from greater than 0 to 5 wt %, from 0.01 to 3 wt %, from 0.1 to 2 wt %, or from 0.1 to 1 wt % of the total weight of the inventive composition.
  • the inventive compositions disclosed herein can comprise at least one lubricant.
  • the lubricant can be used, inter alia, to modify the rheology of the molten inventive compositions, to improve the surface finish of molded articles, and/or to facilitate the dispersion of fillers or pigments. Any lubricant known to a person of ordinary skill in the art may be added to the inventive compositions disclosed herein.
  • Non-limiting examples of suitable lubricants include fatty alcohols and their dicarboxylic acid esters, fatty acid esters of short-chain alcohols, fatty acids, fatty acid amides, metal soaps, oligomeric fatty acid esters, fatty acid esters of long-chain alcohols, montan waxes, polyethylene waxes, polypropylene waxes, natural and synthetic paraffin waxes, fluoropolymers and combinations thereof.
  • lubricants comprise an organopolysiloxane.
  • the organopolysiloxane can have an average molecular weight not less than 40,000 and a viscosity of at least 50.000 cSt.
  • the amount of the lubricant in the inventive composition may be from greater than 0 to 5 wt %; in the alternative, from 0.1 to 4 wt %; or in the alternative, from 0.1 to 3 wt % of the total weight of the inventive composition.
  • Lubricants useful in various embodiments of the invention are disclosed in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001 ).
  • the inventive compositions can include an anti-microbial agent to impede and/or limit the growth of organisms typically encountered in cold and/or wet applications, including bacteriostatic and fungistatic compounds.
  • an anti-microbial agent to impede and/or limit the growth of organisms typically encountered in cold and/or wet applications, including bacteriostatic and fungistatic compounds.
  • anti-microbial agents useful in the invention any one or combination of anti-microbial agents available from The Dow Chemical Company (Midland, Michigan) under the name VINYZENETM, which include blends of dichloro-octyl-isothiazolone; 10,10'-oxybisphenoxarsine; octyl-isothiazolone; and trichlorophenoxyphenol.
  • a blend of zinc pyritione and n- butyl-1,2-benzisothiazonlin-3-one available from PolyChemAlloy (Lenoir, North Carolina) and sold under the name PolySeptTM 2003ZV-HF may be used in the inventive inventive compositions.
  • the inventive compositions may include additives to improve abrasion resistance.
  • the polydimethylsiloxane compositions disclosed in U.S. Patent No. 5,902,854 may be used in certain embodiments of the inventive inventive compositions.
  • the inventive compositions comprise at least one thermoplastic vulcanizates (TPVs), hydrogenated styrenic block copolymers (such as SEBS, or styrene-ethylene ethylene propylene-styrene (SEEPS)), or a combination thereof but not to exceed more than 50 wt% of the total elastomer content of the composition.
  • Thermoplastic elastomers are rubber-like materials that, unlike conventional vulcanized rubbers, can be processed and recycled like thermoplastic materials. When the thermoplastic elastomer contains a vulcanized rubber, it may also be referred to as a thermoplastic vulcanizate (TPV).
  • TPVs are thermoplastic elastomers with a chemically cross-linked rubbery phase, produced by dynamic vulcanization.
  • One measure of this rubbery behavior is that the material will retract to less than 1.5 times its original length within one minute, after being stretched at room temperature to twice its original length and held for one minute before release (ASTM D1566).
  • ASTM D412 Another measure is found in ASTM D412, for the determination of tensile set.
  • the materials are also characterized by high elastic recovery, which refers to the proportion of recovery after deformation and may be quantified as percent recovery after compression.
  • a perfectly elastic material has a recovery of 100% while a perfectly plastic material has no elastic recovery.
  • ASTM D395 for the determination of compression set.
  • a commercial TPV is SATOPRENETM thermoplastic rubber which is manufactured by Advanced Elastomer Systems and is a mixture of crosslinked EPDM ("XL-EPDM”) particles in a crystalline polypropylene matrix.
  • VYRAMTM consisting of a mixture of polypropylene and natural rubber, marketed by Advanced Elastomer Systems.
  • suitable elastomers include KRATONTM, a brand of styrene block copolymer (SBC) marketed by KRATON Polymers, and DYNAFLEXTM, a thermoplastic elastomer marketed by GLS Corporation and which is made with KRATONTM polymer.
  • the ingredients of the inventive compositions i.e., the ethylene/a-olefin interpolymer, the at least one other polymer component, such as the elastomer (e.g., TPV, styrene/ethylene-butene/styrene (SEBS) copolymers), the polyolefin, such as hPP, RCP, LDPE, or HDPE and the optional additives, fillers and oil can be mixed or blended using methods known to a person of ordinary skill in the art, preferably methods that can provide a substantially homogeneous distribution of the polyolefin and/or the additives in the ethylene/a-olefin interpolymer.
  • suitable blending methods include melt blending, solvent blending and extruding.
  • physical blending devices that provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing can be useful in preparing homogenous blends.
  • Both batch and continuous methods of physical blending can be used.
  • Non-limiting examples of batch methods include those methods using mixing equipment available from Brabender (e.g., BRABENDER PREP CENTERTM, available from C.W. Brabender Instruments, Inc., Southhackensack, N.J.) or BANBURYTM internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment.
  • Non-limiting examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding.
  • the additives can be added into an extruder through a feed hopper or feed throat during the extrusion of the ethylene/ ⁇ -olefin interpolymer, the polyolefin or the inventive composition.
  • the mixing or blending of polymers by extrusion has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, N.Y., pages 322-334 (1986 ).
  • the desired amounts of the additives can be added in one charge or multiple charges to the ethylene/a-olefin interpolymer, the polyolefin or the inventive composition. Furthermore, the addition can take place in any order.
  • the additives are first added and mixed or blended with the ethylene/a-olefin interpolymer, and then the additive-containing interpolymer is blended with the polyolefin.
  • the additives are first added and mixed or blended with the polyolefin and then the additive-containing polyolefin is blended with the ethylene/ ⁇ -olefin interpolymer.
  • the ethylene/a-olefin interpolymer is blended with the polyolefin first and then the additives are blended with the inventive composition.
  • the second composition may comprise a combination of two or more embodiments as described herein.
  • the invention further provides an article comprising at least one component formed from an inventive composition.
  • Articles which may be produced from the inventive composition include, for example, gaskets, profiles (including, for example, profiles used for refrigerators and/or freezers), molded articles, overmolded articles, sheeting, and tubing.
  • Some embodiments of an inventive article have a compression set, at 70 °C, less than 70 percent; in the alternative, less than 65%; or in the alternative, less than 60%.
  • the article is a gasket.
  • the article is a profile.
  • composition includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term interpolymer as defined hereinafter.
  • interpolymer refers to polymers prepared by the polymerization of at least two different types of monomers.
  • the generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
  • ethylene/ ⁇ -olefin interpolymer refers to an interpolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the interpolymer), and at least one ⁇ -olefin.
  • ethylene/ ⁇ -olefin copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copolymer), and an ⁇ -olefin, as the only two monomer types.
  • propylene/ ⁇ -olefin interpolymer refers to an interpolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the interpolymer), and at least one ⁇ -olefin.
  • propylene/ ⁇ -olefin copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the copolymer), and an ⁇ -olefin, as the only two monomer types.
  • propylene/ethylene copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the copolymer), and ethylene, as the only two monomer types.
  • compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
  • the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
  • the term “consisting of” excludes any component, step or procedure not specifically delineated or listed.
  • elastomer refers any melt-processable polymer blend or copolymer in which a continuous elastomeric phase domain is reinforced by dispersed hard (glassy or crystalline) phase domains that act as junction points over a limited range of temperature.
  • thermoplastic refers to a material that can be repeatedly made molten (soft) and solidified (hard) through heating and cooling, respectively.
  • si-crystalline polymer refers to polymers having regions of crystalline molecular structure and amorphous regions.
  • elastomeric polymer refers to a thermoplastic elastomer.
  • blend means a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art.
  • pre-compounded refers to the polymer used to make a polymer formulation, prior to any post reactor compounding or modification of such polymer.
  • a polymer may contain small levels of fugitive process oils from processing equipment or from additive slurries, yet still be considered as not containing any oil.
  • oil amount is determined relative to the weight of the polymer. For a "25% oil containing polymer,” a 1 kg sample would comprise 0.2 kg of oil and 0.80 kg of polymer.
  • the polymers designated as "free-flowing" do not preclude the use of a surface additive such as talc or polyethylene powder to enhance the free-flowing nature of the product in use.
  • Test methods utilized in characterizing the components of the inventive and comparative examples include the following tests.
  • Test samples (except for the inventive and comparative examples shown in Table 11) were made on a fully intermeshing co-rotating twin screw extruder manufactured by Krupp Werner Pfleiderer Corporation (Model ZSK-25, a 25-mm screw diameter having a length to diameter ratio of 48:1).
  • the extruder was equipped with two-hole strand die, water bath and pelletizer to produce resin in pellet form.
  • the materials were starve-fed into the extruder using screw type powder feeders.
  • the extruder conditions were zone 1 through zone 7 were 140°C, 190°C, 190°C, 190°C, 190°C, 190°C, 190°C, 190°C, respectively, and 180 °C at the die.
  • RPM of 500 was used with water chiller temperature of 10 °C.
  • Examples in Table 11 were processed using the conditions shown in Table 12.
  • ID inner diameter
  • wall thickness 0.42 mm.
  • the extruded tube profile was air-cooled on a conveyor. Once stabilized, head pressure and torque were measured at various RPMs ranging from 20 to 160. Samples were collected at each RPM. Visual observations were made on the surface roughness and shape retention of the collected samples.
  • Branching distributions are determined by crystallization analysis fractionation (CRYSTAFTM) using a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain.
  • the samples are dissolved in 1,2,4 trichlorobenzene at 160°C (0.66 mg/mL) for 1 hr and stabilized at 95°C for 45 minutes.
  • the sampling temperatures range from 95 to 30°C at a cooling rate of 0.2°C/min.
  • An infrared detector is used to measure the polymer solution concentrations.
  • the cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased.
  • the analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.
  • the CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF Software (Version 2001.b, PolymerChar, Valencia, Spain).
  • the CRYSTAF peak finding routine identifies a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve.
  • the preferred processing parameters are with a temperature limit of 70 °C and with smoothing parameters above the temperature limit of 0.1, and below the temperature limit of 0.3.
  • Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790.
  • Differential Scanning Calorimetry results are determined using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml/min is used. The sample is pressed into a thin film, at 210MPa (30000 psi) for 5 minutes at 175°C, and then air-cooled to room temperature (25°C). The pressed sample (3-10 mg) is then cut into a 6 mm diameter disk, accurately weighed, placed in a light aluminum pan (about 50 mg), and then crimped shut. The thermal behavior of the profile compositions samples is investigated with the following temperature profile. The sample is rapidly heated to 230°C and held isothermal for 3 minutes, in order to remove any previous thermal history.
  • the sample is then cooled to -90°C, at 10°C/min cooling rate, and held at -90°C for 3 minutes.
  • the sample is then heated to 230°C, at 10°C/min. heating rate.
  • the cooling and second heating curves are recorded.
  • the temperature of crystallization is noted as Tc (°C).
  • the DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -40°C and end of melting.
  • the heat of fusion is measured as the area under the melting curve between -40°C and the end of melting using a linear baseline.
  • the DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30°C and end of melting.
  • the heat of fusion is measured as the area under the melting curve between -30°C and the end of melting using a linear baseline.
  • Calibration of the DSC is done as follows. First, a baseline is obtained by running a DSC from -90 °C without any sample in the aluminum DSC pan. Then 7 milligrams of a fresh indium sample is analyzed by heating the sample to 180 °C, cooling the sample to 140 °C at a cooling rate of 10 °C /min followed by keeping the sample isothermally at 140°C for 1 minute, followed by heating the sample from 140 °C to 180 °C at a heating rate of 10 °C per minute.
  • the heat of fusion and the onset of melting of the indium sample are determined and checked to be within 0.5 °C from 156.6 °C for the onset of melting and within 0.5 J/g from 28.71 J/g for the of fusion.
  • deionized water is analyzed by cooling a small drop of fresh sample in the DSC pan from 25°C to -30 C at a cooling rate of 10 °C per minute.
  • the sample is kept isothermally at -30 °C for 2 minutes and heat to 30 °C at a heating rate of 10°C per minute.
  • the onset of melting is determined and checked to be within 0.5 °C from 0 °C.
  • the melting point(s) (Tm) of each polymer sample is determined from the second heat curve obtained from DSC, as described above.
  • the crystallization temperature (Tc) is measured from the first cooling curve
  • the chromatographic system used is a Polymer Laboratories Model PL-210.
  • the column and carousel compartments were operated at 145°C.
  • Four Polymer Laboratories 20-um Mixed-A LS columns were used, with a solvent of 1,2 4 Trichlorobenzene (TCB).
  • TCB 1,2 4 Trichlorobenzene
  • the samples were prepared at a concentration of 0.1 g of polymer in 50 ml of solvent.
  • the solvent contained 200 ppm of the antioxidant butylated hydroxytoluene (BHT). Samples were prepared by agitating lightly for 1-2 hours at 160°C.
  • the injection volume was 200 microliters and the flow rate was 1.0 ml/min.
  • Analytical temperature rising elution fractionation (ATREF) analysis is conducted according to the method described in U.S. Patent No. 4,798,081 , and Wilde, L.; Ryle, T.R.; Knobeloch, D.C.; Peat, I.R.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982 ).
  • the composition to be analyzed is dissolved in trichlorobenzene, and allowed to crystallize in a column containing an inert support (stainless steel shot), by slowly reducing the temperature to 20°C, at a cooling rate of 0.1°C/min.
  • the column is equipped with an infrared detector.
  • An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column, by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120°C, at a rate of 1.5°C/min.
  • eluting solvent trichlorobenzene
  • the samples are prepared by adding approximately "3g of a 50/50 mixture of tetrachloroethane-d 2 /orthodichlorobenzene" to" 0.4 g sample" in a 10 mm NMR tube.
  • the samples are dissolved and homogenized by heating the tube and its contents to 150°C.
  • the data are collected using a JEOL EclipseTM 400MHz spectrometer or a Varian Unity PlusTM 400MHz spectrometer, corresponding to a 13 C resonance frequency of 100.5 MHz.
  • the data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together.
  • the spectral width is 25,000 Hz with a minimum file size of 32K data points.
  • the samples are analyzed at 130°C in a 10 mm broad band probe.
  • the comonomer incorporation is determined using Randall's triad method ( Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989 ).
  • the ethylene/ ⁇ -olefin multiblock copolymers are characterized by an average block index, ABI, which is greater than zero and up to 1.0 and a molecular weight distribution, M w /M n , greater than 1.3.
  • the average block index, ABI is the weight average of the block index ("BI") for each of the polymer fractions obtained in preparative TREF (i.e., fractionation of a polymer by Temperature Rising Elution Fractionation) from 20°C and 110°C, with an increment of 5°C (although other temperature increments, such as 1°C, 2°C, 10°C, also can be used):
  • ABI ⁇ w i B I i
  • BI i is the block index for the ith fraction of the inventive ethylene/ ⁇ -olefin interpolymer obtained in preparative TREF
  • w i is the weight percentage of the ith fraction.
  • the square root of the second moment about the mean hereinafter referred to as the second moment weight average block index, can be defined as follows.
  • 2 nd moment weight average BI ⁇ w i B I i ⁇ ABI 2 N ⁇ 1 ⁇ w i N , where N is defined as the number of fractions with BI i greater than zero.
  • ATREF i.e., analytical TREF
  • P X is the ethylene mole fraction for the ith fraction, which can be measured by NMR or IR as described below.
  • T A and P A are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments” (which refer to the crystalline segments of the interpolymer). As an approximation or for polymers where the "hard segment" composition is unknown, the T A and P A values are set to those for high density polyethylene homopolymer.
  • T AB is the ATREF elution temperature for a random copolymer of the same composition (having an ethylene mole fraction of P AB ) and molecular weight as the olefin block copolymer.
  • T ATREF is the analytical TREF elution temperature for narrow composition random copolymers and/or preparative TREF fractions of broad composition random copolymers.
  • T XO is the ATREF temperature for a random copolymer of the same composition (i.e., the same comonomer type and content) and the same molecular weight and having an ethylene mole fraction of P X .
  • TMA Thermal Mechanical Analysis
  • Rheology was measured using Dynamic Mechanical Spectroscopy (DMS). DMS experiments were conducted at 190°C on a Rheometrics ARES equipped with 25 mm parallel plates. Sample discs (25 mm in diameter) were cut from the injection molded plaques and nitrogen purge. The frequency was varied between 0.1 and 100 rad/s. The strain amplitude was adjusted based upon the response of the samples between 4 and 10 %. Rheology ratio (RR) was calculated as the ratio of the complex viscosity at 0.1 rad/s to complex viscosity at 100 rad/s. The tan ⁇ which is a ratio of the loss modulus (G") to the storage modulus (G') was characterized at 0.1 rad/s.
  • DMS Dynamic Mechanical Spectroscopy
  • Density (g/cm 3 ) was measured according to ASTM-D 792-03, Method B, in isopropanol. Specimens were measured within 1 hour of molding after conditioning in the isopropanol bath at 23°C for 8 minutes, to achieve thermal equilibrium prior to measurement. The test specimens were compression molded according to ASTM D-4703-00 Annex A with a 5 min initial heating period at about 190°C and a 15°C/min cooling rate per Procedure C. The specimen was cooled to 45°C in the press with continued cooling until "cool to the touch.”
  • Melt index (I 2 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/2.16 kg.
  • Melt index (I 5 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/5.0 kg.
  • Melt index (I 10 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/10.0 kg.
  • High load melt index (I 21 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/21.0 kg.
  • the melt flow rate (MFR) is measured in accordance with ASTM D-1238-04, condition 230°C/2.16 kg.
  • Shore A hardness was measured per ASTM D2240 on injection molded plaques of 0.32 cm thickness. This test method permits hardness measurements based on either initial indentation or indentation after a specified period of time, or both. As used herein , the indentation was measured at a specified time of 10 seconds.
  • Tensile strength and elongation at break was measured using ASTM D 1708 which is a micro-tensile method with a pull rate of 12.7cm (5 inches) minute in the flow direction of the injection molded plaque.
  • the dimensions of the injection molded plaque were 101.6 mm x 152.4 x 3.2 mm.
  • Compression set was measured according to ASTM D-395 at 23°C, 40°C and 70°C.
  • the sample was prepared by stacking 25.4 mm diameter round discs cut from 0.318cm (0.125 inch) thick injection molded plaques until a total thickness of 12.7 mm is reached.
  • Injection molding was carried out on an Arburg 370C-80 ton injection molder using a plaque mold that is 101.6 mm x 152.4 x 3.2 mm.
  • Typical process conditions for sample preparation include the following: Barrel and Mold Temperatures, zones 1 through 4 and nozzle at 205°C and mold at 15°C; Extruder conditions of RPM 30 (m/min), back pressure of 1500kPa (15 bar) dosage of 70 cubic centimeters (cc), and real dosage of 72 cc; Optimal Injection parameters of injection speed of 25 cc/seconds, transfer position of 15 cc, pressure at transfer of 32700kPa (327 bar) fill time of 2.37 seconds, and cushion of 7.1 cc; hold conditions of pressure at 30000kPa (300 bar) hold time of 40 seconds, cool time of 20 seconds, dosage time of 7.2 seconds and a cycle time of 68.8 seconds.
  • compression set after 24 hours (h) at 40 °C or 60 °C at 25% strain is reported based on ISO 815- Type B method using 13 mm round disks, 6 mm thick. Samples cut from injection molded plaques (0.125" thick) are stacked up to a thickness of 6mm.
  • Normalized oil-bleed index is an optical measurement to compare oil-bleed characteristics. Molded plaques are aged for 3 weeks (at 23°C and 70°C) while resting on sheets of ZigZagTM cigarette paper. After aging, the cigarette paper is removed and optically scanned against a black background to measure the extent of oil-bleed. The scanning is performed using the Xerox WorkCentreTM M118i copier/fax/scanner. The image is scanned in "Text" mode at 200dpi, and saved as a TIFF file. The TIFF file is opened in MS Paintbrush, cropped on two sides, then saved. The image is then opened in Photoshop CS2 (v.9) and cropped on the other two sides.
  • grayscale histogram It is then converted to an 8-bit grayscale image so that a grayscale histogram can be created.
  • the grayscale image is then analyzed using the Photoshop software to create a histogram showing the percentile of each of 4 quadrants of grayscale, ranging from 0 (black) to 255 (white).
  • the average grayscale percentile is recorded. For example, if 1% of the pixels are in the 0-64 level of grayscale quadrant, and 3% of the pixels are in the 65-128 level of grayscale quadrant, and 15% are in the 129-192 level of grayscale quadrant, and 31% are in the 193-255 level of grayscale quadrant, the system calculates the average to be 12.5%.
  • the tack force was measured using a ChemInstruments EZ Lab, Compatible Loop Tack Tester (Model LT-1000).
  • the test sample was an injection molded or compression molded bar 10.16cm x 15.24cm x 0.318cm (4 inch x 6 inch x 0.125 inch)"
  • five bars were tested, and an average recorded.
  • test bars were conditioned at 70°C for seven days, in a forced air convention oven, before being tested for tack.
  • the test method was based on a modified version of ASTM D6195-03, " Standard Test Methods for Loop Tack" (Reference: 3 Annual Book of ASTM Standards, Vol 15.06 .).
  • a bar was placed in the lower brace of the loop tack tester.
  • a strip of "127 ⁇ m (5 mil) thick" MYLAR (2.54cm x 15.24cm) (1 inch x 6 inch) was cut, using a 2.54cm x 15.24cm ("1 inch x 6 inch”) die.
  • the end of the MYLAR strip was trimmed to form a 2.54cm x 12.7cm ("1 inch x 5 inch”) strip.
  • the MYLAR strip was folded into a loop, with the glossy side as the exterior side, and place in the top grip of the Loop Tack tester.
  • the exterior surface of the loop was brought into controlled contact with a 2.54cm x 2.54cm ("1 inch x 1 inch”) surface of test bar specimen, with the only force applied being the weight of the MYLAR strip itself.
  • the MYLAR strip was then removed from the substrate, and the force to remove the MYLAR strip from the contacting surface was measured by a recording instrument.
  • Polymer Mooney viscosity (ML 1+4 at 125°C) was measured in accordance with ASTM 1646-04, with a one minute preheat time and a four minute rotor operation time.
  • the instrument is an Alpha Technologies Rheometer MDR.
  • NORDEL IP Hydrocarbon Rubbers ENGAGE Polyolefin Elastomers, VERSIFY Elastomers and Plastomers and INFUSE Olefin Block Copolymers are available from The Dow Chemical Company;
  • PROFAX resins are available from Lyondellbasell Industries N.V. (Rotterdam, Netherlands), and LUPEROX compounds are organic peroxides available from Arkema, Inc. (Philadelphia, PA).
  • Table 7 provides the components for the formulations shown in Tables 8-10.
  • Table 8 provides the formulations for Inventive Examples 15-16 and Comparative Examples 14 and R-S. Each of the Inventive and Comparative Examples in Table 8 include 72.5 PHR oil.
  • Table 9 provides the formulations for Inventive Examples 18-19 and Comparative Examples 17 and T-U. Each of the Inventive and Comparative Examples in Table 9 include 130 PHR oil.
  • Table 10 provides the formulations for Inventive Examples 21-22 and Comparative Examples 20 and V-W. Each of the Inventive and Comparative Examples in Table 10 include 190 PHR oil.
  • Table 11 provides the formulations of Inventive Examples 23-26 and X and Comparative Example Y. All quantities in Table 11 are in weight percentages.
  • Table 12 provides the extruder conditions for the samples of the Inventive and Comparative Examples of Table 11 that were prepared on a ZSK-30 twin screw extruder with dual injector ports.
  • Table 13 provides the characteristics of Inventive Examples 23-26 and X and Comparative Example Y.
  • **R07 is a diene free, single reactor, ethylene/propylene copolymer (EP) containing 66 wt% ethylene and having a Mooney Viscosity of 70.
  • ***R08 is a diene free single reactor EP containing 71 wt% ethylene and having a Mooney Viscosity of 70. ⁇ ML (1+4), 125 °C).
  • # RR indicates the rheology ratio (V0.1/V100), 190 C. ## Oil extended polymer. a) Mooney Viscosity of 70 and 70 wt% Ethylene. b) Mooney Viscosity of 85 and 68 wt% Ethylene. Table 8 Comp. Ex. R Comp. Ex. 14 Comp. Ex.
  • Comparative examples R, T and V use an EP rubber with delta H less than 36 J/g with a tack force in the final article form IS greater than 0.012 N that is unacceptable from a tack perception.
  • Comparative Examples S and U use an EP rubber with a Mooney viscosity close to 20, which is less than the preferred range of greater than 55. The NOBI for these samples, S and U, is unacceptable as such low Mooney polymers are unable to hold high levels of oil.
  • Comparative Example W uses VISTALLON 3666 containing 75 phr of oil that is supplied as a bale rather than pellets, and is not the preferred route for Thermoplastic Extrusion compounders.
  • Inventive Examples 15, 16, 18, 19, 21 and 22, on the other hand are formulations containing ethylene/ ⁇ -olefin interpolymers having a ⁇ Hf greater than 36 J/g, and a Mooney viscosity greater than 55, and also containing an HDPE. These compositions also have rheology ratio greater than 25.
  • the Inventive Example formulations have the right balance of shore A hardness, compression set at elevated temperatures, low tack, low oil bleed, tensile strength, elongation, and TMA.
  • Comparative Example R exhibits a tack force that is too high (note that the ⁇ Hf of R07 is 34 J/g ⁇ Hf).
  • Comparative Example S includes R04 which has a Mooney viscosity less than 55. Comparative Example S also had a high tack force.
  • Inventive Examples 22-26 are formulations with an EPDM having a ⁇ Hf greater than 36 J/g and a Mooney viscosity greater than 55 as component A, and a HDPE as component B. These formulations also have a rheology ratio greater than 25. These inventive compositions exhibit the inventive balance of shore A hardness, compression set at elevated temperatures, low tack, low oil bleed, tensile strength and elongation. Comparative Example Y that has no HDPE and underwent a distortion in shape. Example X had NOBI values of 100 indicating significant oil bleed. The remaining Comparative Examples did not have an optimum balance of properties.
  • Inventive Example 27 contained EPDM 1/HDPE 1 (75/25 or 3/1 ratio) + 1 wt% PDMS (MB50-002) was prepared using a continuous mixer.
  • the EPDM 1 had a Mooney Viscosity (ML (1+4) at 125°C) of 70, a ⁇ Hf of 39.4 and a MWD of 3.04.
  • the HPDE 1 has a density of 0.954 g/cc and a melt index (I 2 ) of 20 g/10 min.
  • Inventive Example 27 was formed in a Farrel CP 250 continuous mixer.
  • the mixer was equipped with the 2.88 inch, 7/7 rotor combination with two dams at the 4 and 5 positions and a vent in the middle of the 7/8 position.
  • the EPDM 1 (74.25 wt%) and HDPE 1 (24.75%) and PDMS (MB50-002 MASTERBATCH) (1%, based on the total composition weight)) were fed via loss and weigh feeders, and the polymers were melted and compounded in the mixer.
  • the residence time was controlled by a feed rate at 136.1 kg (300 pounds) per hour, orifice opening of 45-65%, and a mixer rotor speed of 300-450 RPM.
  • the mixer conditions are shown in Table 14.
  • Table 14: Mixer Conditions (Melt Temp. 225°C) Orifice Chamber Body Feed Hopper Set Point Temp. (°C) 150 150 50 Actual Temp. (°C) 165 142 99
  • Table 16 Freq G' G" Eta* tan_delta Temp Torque Strain G* Phase Angle rad/s Pa Pa Pa-s °C g-cm % Pa ° 0.1 4083.79 5242.94 66457.3 1.28384 190 20.6942 9.95353 6645.73 52.084 0.15849 5438.59 6790.37 54892.4 1.24855 189.99 27.0804 9.94977 8699.85 51.308 0.25119 7157.69 8759.15 45032.8 1.22374 190 35.191 9.9443 11311.7 50.745 0.39811 9353.63 11267.9 36784.8 1.20465 190 45.527 9.93737 14644.3 50.303 0.63096 12218.6 14566.5 30132.8 1.19216 190 59.0536 9.92835 19012.5 50.01 1 15932.6 18727.2 24587.7 1.1754 190

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Claims (6)

  1. Une composition comprenant :
    i) un constituant C, un interpolymère d'éthylène/α-oléfine
    l'interpolymère ayant une viscosité Mooney (ML 1+4, 125 °C) supérieure ou égale à 55 et un ΔHf supérieur ou égal à 36 J/g ; et
    ii) un constituant D, un polyéthylène haute densité (HDPE) ;
    le HDPE ayant un I2 allant de 1 à 50 g/10 min, tel que mesuré par l'ASTM D-1238-04, condition 190 °C/2,16 kg ; et
    l'interpolymère d'éthylène/α-oléfine étant un interpolymère d'éthylène/α-oléfine/diène ;
    l'interpolymère d'éthylène/α-oléfine/diène ayant un rapport rhéologique (V0,1/V100), à 190 °C, supérieur ou égal à 25 ; et
    la composition n'incluant pas d'agent de vulcanisation ou de co-agent de vulcanisation.
  2. La composition de la revendication 1, dans laquelle le constituant C a une MWD inférieure à 4.
  3. La composition de la revendication 1, dans laquelle le HDPE est présent en une quantité allant de 30 à 100 PHR, rapporté au poids de l'interpolymère d'éthylène/α-oléfine.
  4. La composition de n'importe laquelle des revendications précédentes, la composition ayant une déformation rémanente à la compression, à 70 °C, inférieure à 70 pour cent, telle que mesurée par l'ASTM D-395.
  5. Un article comprenant au moins un constituant formé à partir de la composition de n'importe laquelle des revendications précédentes.
  6. L'article de la revendication 5, l'article ayant une force de pégosité inférieure ou égale à 0,012 N, telle que mesurée par une version modifiée de l'ASTM D6195-03, « Standard Test Methods for Loop Tack » (Référence 3 : « Annual Book of ASTM Standards », Vol. 15.06).
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US20130303680A1 (en) 2013-11-14
JP2013527251A (ja) 2013-06-27
KR20120101683A (ko) 2012-09-14
BR112012011927A2 (pt) 2020-09-24
KR101760845B1 (ko) 2017-07-25
EP2501758A1 (fr) 2012-09-26
EP3467024B1 (fr) 2022-08-03
EP3467024A1 (fr) 2019-04-10
CN102712797B (zh) 2016-10-12
JP5865254B2 (ja) 2016-02-17
US9273203B2 (en) 2016-03-01
CN102712797A (zh) 2012-10-03
US8829106B2 (en) 2014-09-09
WO2011062809A1 (fr) 2011-05-26

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